DFT studies of disubstituted diphenyldithiophosphates of nickel(II): Structural and some spectral parameters

Abstract

Three nickel(II) disubstituted diphenyldithiophosphate complexes corresponding to [{(ArO)2PS2}2Ni] [Ar = 2,4-(CH3)2C6H3 (1), 3,5-(CH3)2C6H3 (2) and 4-Cl-3-CH3C6H3 (3)] were theoretically compared to the experimentally reported spectroscopic and X-ray diffraction data. The complexes were computationally studied by using density functional theory (DFT) in its hybrid form B3LYP. The complexes were optimized to calculate the different parameters, vibrational bands and NMR theoretically. The conformational analysis has been performed to determine the stable conformers of complexes. In theses complexes the ligands are coordinated to the nickel metal ion as a bidentate chelating agent via the two thiolate sulfur atoms leading to square planar geometry. The energy gaps of frontier orbital (HOMO–LUMO) have also been calculated along with the global reactivity descriptors quantum parameters. The calculated geometric and spectral results reproduced the experimental data with well agreement. Theoretical calculated molecular orbitals (HOMO–LUMO) and their energies have been calculated that suggest charge transfer occurs within the complexes. The electrophilic and nucleophilic sites are theoretically evaluated by molecular electrostatic potential.